CN103415502A - Chelating agent precursors, fluids containing them, and their use - Google Patents
Chelating agent precursors, fluids containing them, and their use Download PDFInfo
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- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
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- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
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- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
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Abstract
The present invention relates to a chelating agent precursor that contains glutamic acid N,N-diacetic acid (GLDA) and/or methylglycine N,N-diacetic acid (MGDA) wherein at least one of the carboxylic acid groups is presentas a carboxylic acid derivative selected from the group of amides, anhydrides, and esters, combinations thereof, and salts thereof, provided that it is not the triethyl ester of GLDA, the triethyl mono-t-butyl ester of GLDA, the tri-t-butyl ester of GLDA, the monobenzyl tri-t-butyl ester of GLDA, any ester or amide that contains azacycloalkane groups, any amide that contains biotin groups, any amide that contains minoethylcarbamoyl based amide groups, (S)-diethyl 2,2'-(1-benzyloxy)-1,5-dioxo-5-(prop-2-ynylamino)pentan-2-ylazanediyl-diacetate, diethyl 2,2'-(5-(3-azidopropylamino)-1-(benzyloxy)-1,5-dioxo-pentan-2-ylazanediyl-diacetate, the trimethyl ester of MGDA, the monomethyl ester dimethylamide of MGDA, the dibenzyl ester of MGDA, the dibenzyl mono t-butyl ester of MGDA, the di t-butyl ester of MGDA, the di-t-butyl- monobenzyl ester of MGDA, N,N-bis(benzyloxycarbonylmethyl)-N'-methoxycarbonylmethyl-alanine amide, or N,N- bis(tert-butoxycarbonyl)-N'-methoxycarbonylmethyl-alanine amide, and esters of GLDA immobilized on a gel, and that the amide is not the amide of ammonia, to a fluid containing the above chelating precursor and a liquid, and to the use of a chelating agent precursor of MGDA and GLDA and fluids containing them in an application wherein delayed acidity or chelating capacity is useful, such as in descaling, bleaching, cleaning, and treating oil and/or gas-containing subterranean formations.
Description
The present invention relates to have the acidity of delay and the solution/fluid of sequestering power, described solution/fluid contains sequestrant L-glutamic acid Ν, Ν-oxalic acid (GLDA) and/or methylglycine Ν, the precursor of Ν-oxalic acid (MGDA), the invention still further relates to the sequestrant precursor, and relate to the purposes of described fluid and the purposes of described sequestrant precursor.
Therefore contain the precursor of amino polycarboxylic acid and have the acidity of delay and the solution of sequestering power is well known in the art.US2005/0056423 discloses the fluid that is applicable to remove the filter cake that contains carboxylicesters and this esterolytic alkali of energy catalysis.Described ester is selected from some ester of ethylenediamine tetraacetic acid (EDTA).
Yet, in this area, the improvement fluids of the different hydrolysis distribution curves of having of acidity that delay is provided and sequestering power existed to demand.
Have now found that, wherein at least one hydroxy-acid group is ester, and the GLDA of acid anhydrides or acid amides rather than carboxylic acid or carboxylate groups or the precursor of MGDA have the hydrolysis distribution curve different from ester class as known in the art, and simultaneously, it presents good anticorrosive curve.In the present invention, have been found that in addition the molecule for the special applications preparation customization of the controllable release of wherein expecting sequestrant is possible.Finally, the sequestrant molecule (these molecules are respectively alcohol, carboxylic acid or amine) that reacts with it to produce ester, acid anhydrides or acid amides can be selected by this way: functional compound can be added to the fluid for specific purposes.
Therefore, the invention provides sequestrant L-glutamic acid Ν, Ν-oxalic acid (GLDA) and/or methylglycine N, the sequestrant precursor of N-oxalic acid (MGDA), wherein, at least one hydroxy-acid group exists with carboxylic acid derivative, and described carboxylic acid derivative selects free acid amides, acid anhydrides and ester, its combination, and the group of salt composition, condition is that described sequestrant precursor is not the triethyl of GLDA, the triethyl list tertiary butyl ester of GLDA, the tri-tert ester of GLDA, the monobenzyl tri-tert ester of GLDA, the any ester or the acid amides that contain the azacycloalkyl hydrocarbyl group, the any acid amides that contains the vitamin H group, contain any acid amides based on the amide group of aminoethylamino formyl radical, (S)-2,2 '-(1-benzyloxy)-1,5-dioxo-5-(Propargyl amino) penta-2-base azane two bases-oxalic acid diethyl ester, 2,2 '-(5-(3-azido-propyl group amino)-1-(benzyloxy)-1,5-dioxo-penta-2-base azane, two bases-oxalic acid diethyl ester, the trimethyl of MGDA, the monomethyl ester dimethylformamide of MGDA, the dibenzyl ester of MGDA, the dibenzyl list tertiary butyl ester of MGDA, the di-t-butyl ester of MGDA, the di-t-butyl monobenzyl ester of MGDA, N, two (benzyloxycarbonyl the methyl)-N ' of N--methoxycarbonyl methyl-ala amide or N, two (uncle-butoxy carbonyl)-N ' of N--methoxycarbonyl methyl-ala amide and the ester that is fixed on the GLDA on gel, and described acid amides is not the acid amides of ammonia.
The present invention has got rid of MGDA and GLDA ester and the acid amides of describing in the prior art file especially, such as the people such as WO2004/087284, WO2006/013042, WO2008/145609 and S.Lata at " High-affinity Adaptors for switchable recognition of histidine-tagged proteins, " JACS, Vol.127, No.29, the monobenzyl tri-tert ester of the tri-tert ester of the triethyl list tertiary butyl ester of the triethyl of disclosed GLDA, GLDA, GLDA, GLDA in 2005, pp.10205-10215, as such as people such as A.Grauer at " Synthetic receptors for the differentiation of phosphorylated peptide with nanomolar affinities, " Chemistry a European Journal Vol.14, No.29, October10, 2008, in pp.8922-8927, the people such as C.Liu are at " Convergent and Sequential Synthesis of Dendritic, Multivalent Complexing Agents ", Synthesis2002, No.10, in pp.1398-1406, the people such as S.Lata are at " High-affinity Adaptors for switchable recognition of histidine-tagged proteins, " JACS, Vol.127, No.29, 2005, in pp.10205-10215, the disclosed azacycloalkyl hydrocarbyl group that contains in WO2008/145609 or WO2006/013042, for example any ester or the acid amides of tetraazacyclododecanand group, as such as the people such as E.Drakopoulou disclosed any acid amides that contains the vitamin H group in " Design and synthesis of multifunctional phospholipids, " Tetrahedron Letters41 (2000) pp.4131-4143, by people such as Grauer at " Synthetic receptors for the differentiation of phosphorylated peptide with nanomolar affinities, " Chemistry a European Journal Vol.14, No.29, October10, 2008, the disclosed any acid amides contained based on the amide group of aminoethylamino formyl radical in pp.8922-8927, (S)-2, 2 '-(1-benzyloxy)-1, 5-dioxo-5-(Propargyl amino) penta-2-base azane two bases-oxalic acid diethyl ester, 2, 2 '-(5-(3-azido-propyl group amino)-1-(benzyloxy)-1, 5-dioxo-penta-2-base azane, two bases-oxalic acid diethyl ester, the ester of GLDA, the people such as Ohtani at " Five-coordinated complexes containing an optically active ligand, " Chemistry Letters, Chemical Society of Japan, January1,1980, pp.465, the trimethylammonium ester of disclosed MGDA and the monomethyl ester dimethylformamide of MGDA in 466, as people such as C.W.Grote at " Stereocontrolled Synthesis of DTPA analogues branched in the ethylene unit, " Journal of Organic Chemistry, Am Chem Soc, Vol.60, No.21, January1, the dibenzyl ester of disclosed MGDA in 1995, the dibenzyl list tertiary butyl ester of MGDA, the di-t-butyl monobenzyl ester of the di-t-butyl ester of MGDA and MGDA, N, two (benzyloxycarbonyl the methyl)-N ' of N--methoxycarbonyl methyl-ala amide or N, two (uncle-butoxy carbonyl)-N ' of N--methoxycarbonyl methyl-ala amide, and as the disclosed ester that is fixed on the GLDA on gel in WO2004/087284.
In above-mentioned prior art document, all do not disclose described GLDA and MGDA ester and acid amides and have the useful purposes as the precursor of GLDA and MGDA; They or with the intermediate in synthetic route, be disclosed, or opened in diverse field and have benefit by sky, for example, as the acceptor of peptide or albumen.
Finally, it should be understood that the present invention does not cover the acid amides of GLDA and/or MGDA and ammonia.
In addition, the invention provides the fluid that contains above-mentioned GLDA and/or MGDA acid amides, ester and/or acid anhydrides and liquid, wherein said liquid is preferably liquid, aqueous.The meaning of fluid comprises solution, suspension and emulsion; Preferably, they are solution.
Finally, the present invention relates to the purposes in the application of the acidity of the fluid expected delay therein that is selected from the sequestrant precursor of GLDA ester, acid amides and acid anhydrides and MGDA acid amides, ester and acid anhydrides (being GLDA and MGDA precursor) or contains one or more these precursors and/or sequestering power, described application examples as for descaling, bleach, clean and process the subterranean strata of oil-containing and/or gas.
It should be pointed out that in WO2009/024519 and disclose the purposes of GLDA acid amides in field use, wherein said acid amides is the acid amides that can be prepared by one or more hydroxy-acid groups and ammonia react, and it discloses these GLDA acid amides and can be hydrolyzed to GLDA.Yet the purposes in field use is to be mentioned in numerous purposes, it does not illustrate, and is not given in the benefit of using acid amides in described application-specific yet.The GLDA obtained by GLDA or MGDA and ammonia react or the acid amides of MGDA will not have special advantage in some applications, because during the hydrolysis of these precursors, ammonia will dissociate out, it can become the nutrition of unwelcome microorganism, therefore, not too preferred these acid amides.
Wherein at least one hydroxy-acid group is ester, acid anhydrides or acid amides, rather than the precursor of the GLDA of carboxylic acid or carboxylate groups or MGDA has the hydrolysis distribution curve different from ester as known in the art really.At first, MGDA and GLDA are the molecules with chemically different hydroxy-acid groups, and in EDTA, all hydroxy-acid groups are all identical.Therefore, under identical condition, the hydrolysis of MGDA and GLDA precursor is larger and slower than the hydrolysis of EDTA precursor with the hydrolysis difference of EDTA precursor.In addition, compare with the EDTA ester of prior art, find that a lot of GLDA esters are to have enough low viscosity and the high fluid of density ratio water.This causes some advantages.At first, this means that they can be pumped to subterranean strata.If they are pumped in aqueous fluid, they will be sink to the bottom of aqueous fluid and have an effect in described rock stratum, and in described rock stratum, they slowly are hydrolyzed to acid GLDA molecule and alcohol.In addition, the present invention also provides acid amides and the acid anhydrides of sequestrant MGDA and GLDA, compares with ester, and it has other hydrolysis distribution curve, and this makes as special applications customizes molecule becomes possibility.Usually, acid anhydrides tends to more easily be hydrolyzed than ester, and acid amides certainly, is hydrolyzed accurately distribution curve and will depends on the concrete selection that is present in alcohol, amine and/or carboxylic acid in GLDA and/or MGDA precursor than usually more difficult hydrolysis of ester.Therefore, depend on needs much degree delayed releases acidity and sequestering power, can in molecular designing, carry out optimal selection.On the other hand more favourable than EDTA ester: sequestrant precursor of the present invention is easier to hydrolysis under acidic conditions, because the EDTA(of acid form and NTA) in aqueous fluid, be insoluble,practically, and it also can produce the precipitation of not expecting.Finally, in described sequestrant precursor, provide the molecule (described molecule is respectively alcohol, carboxylic acid or amine) of ester, acid anhydrides or acid amides to select by this way: for specific purpose, functional compound can be added, and they are being released in hydrolysing step together with GLDA and/or MGDA.
In this application, term " is processed the subterranean strata of oil-containing and/or gas " and is referred to any processing of having contained described rock stratum.It has been contained especially and has processed described rock stratum to realize at least one in following purpose: the perviousness (i) increased, (ii) short grained removal, and (iii) removal of inorganic scale, and strengthen thus the well performance and make from oil and/or the gas increase of described rock stratum, producing/reclaiming.Simultaneously its can contain clean well and to oil/gas production well until produce equipment and comprise the refinery de-sludging.The application of sequestrant precursor in processing subterranean strata is useful especially, because particularly in this purposes, realize the delay of chemical (as sequestrant and alcohol, amine or carboxylic acid) available be useful, therefore they will more in depth play a role in described rock stratum, and can not exhaust in the stage too morning for the treatment of processes.In addition, in processing subterranean strata, it is particularly advantageous discharging slowly because have been found that described rock stratum component (normally carbonate) slowly be dissolved in the best permeability of generation when not destroying described rock stratum.Therefore, the method for processing subterranean strata is contained in the present invention especially, in described method, the sequestrant precursor of GLDA or MGDA or the fluid that contains such sequestrant precursor is introduced in described rock stratum.
In the method, during the processing of described rock stratum, when the sequestrant precursor is introduced in described rock stratum or afterwards, the sequestrant precursor can be hydrolyzed at least partly.
Even more preferably, the purposes of described sequestrant precursor in the processing of subterranean strata contained in the present invention, wherein said sequestrant precursor carboxylic acid derivative is the ester of C1-C6 alcohol or C1-C6 glycol, wherein said sequestrant precursor is hydrolysis at least partly in described rock stratum, and described alcohol or glycol are released, and help in some embodiments hydrate to suppress and/or serve as mutual solvent.
In another embodiment, in processing the method for rock stratum, described fluid contain in addition help the sequestrant precursor hydrolysis to discharge the reagent of GLDA and/or MGDA, as enzyme, alkali or acid.
Preferably, in the processing of subterranean strata, the sequestrant precursor is the ester of GLDA, even more preferably, is the ester of GLDA and C1-C6 alcohol or C1-C6 glycol, most preferably, is the ester of GLDA and C2-C6 alcohol or C2-C6 glycol.
In the embodiment of the method for processing subterranean strata, contain the pH of fluid of sequestrant precursor preferably between 1-7, and in another embodiment, subterranean strata contacts with the temperature of described fluid between 25 ℃ to 204 ℃, even more preferably, between 25 to 149 ℃, the most preferably contact of the temperature between 65 to 149 ℃.
Sequestrant precursor of the present invention contains in the embodiment of one or more ester groups therein, and these ester groups can be derived from GLDA and/or MGDA and pure reacting.Described alcohol can contain one or more other groups such as aromatic group, amine groups, ether group, ester group, phosphorus-containing groups, sulfur-containing group, amide group and oh group.Preferably, described alcohol is the fatty alcohol that contains 1 to 12 carbon atom, and described alcohol optionally can contain extra hydroxyl, amine and/or ether group.In still another preferred embodiment, described alcohol contains uncle or secondary hydroxy group.Even more preferably, described alcohol is selected from lower alcohol, and as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, these alcohol can be straight chain or branching; Glycol such as ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, ethylene glycol monobutyl ether (EGMBE), neopentyl glycol, polyoxyethylene glycol, polypropylene glycol, based on multipolymer of polyoxyethylene glycol and polypropylene glycol etc., and glycol ethers such as 2-methyl cellosolve, diethylene glycol monomethyl ether; Glycerine, hydroxyl propyl alcohol, tetramethylolmethane, 1,1,1-TriMethylolPropane(TMP), 1,1,1-trimethylolethane, 1,2,3-TriMethylolPropane(TMP), two-TriMethylolPropane(TMP), Dipentaerythritol, 2-butyl-2-ethyl-1,3-PD, 1,6-hexane diol, cyclohexanedimethanol; Rudimentary amino alcohol such as monoethanolamine, aminopropanol, amino butanol; Alcohol alcoxylates, preferably ethoxylated alcohol.
Mixed ester is also contained in the present invention, that is, and and the ester of MGDA and/or GLDA and two or more different alcohol.
Sequestrant precursor of the present invention contains in the embodiment of one or more amide groups therein, and these amide groups can reacting derived from GLDA and/or MGDA and amine.Described amine can contain one or more other groups such as aromatic group, amine groups, ether group, ester group, amide group, phosphorus-containing groups, sulfur-containing group and oh group.Preferably, described amine is the aliphatic amine that contains 1 to 12 carbon atom, and described amine optionally can contain extra hydroxyl, carboxylic acid, amine and/or ether group.In another preferred embodiment, described amine contains uncle or secondary amino group.Even more preferably, described amine is selected from low-grade amine, as aminomethane, ethylamine, aminopropane, aminobutane, aminopentane, aminohexane, amino heptane, amino-octane, amino nonane, amino decane, these amine can be straight chain or branching; Rudimentary amino alcohol such as monoethanolamine, aminopropanol, amino butanol; Oxyalkylated amine, the preferably amine of ethoxylation; Well known to a person skilled in the art amino acid, as natural amino acid.
The mixing acid amides is also contained in the present invention, that is, and and the acid amides of MGDA and/or GLDA and two or more different amine.
Sequestrant precursor of the present invention contains in the embodiment of one or more anhydride groups therein, and these anhydride groups can reacting derived from GLDA and/or MGDA and carboxylic acid.Described carboxylic acid can contain one or more other groups such as aromatic group, amine groups, ether group, ester group, amide group, phosphorus-containing groups, sulfur-containing group and oh group.
Preferably, described carboxylic acid is lipid acid or the aliphatic carboxylic acid that contains 1 to 12 carbon atom, and described carboxylic acid optionally can contain extra hydroxyl, amine, carboxylic acid and/or ether group.Even more preferably, described carboxylic acid is selected from the low-grade carboxylic acid, and as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, these acid can be straight chain or branching, oxyacetic acid, be selected from and well known to a person skilled in the art lipid acid, as lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, oleic acid (oleic acid), oleic acid (oleinic acid), linolic acid, α-linolic acid, gamma-linoleic acid, Oleomyristic acid, arachidonic acid, sapienic acid, erucic acid, Zoomeric acid, cis-9-20 carbon acid, cetoleic acid, undecylenic acid, punicic acid, or derived from rapeseed oil, Viscotrol C, safflower oil, linseed oil, soya-bean oil, sesame oil, poppyseed oil, perilla oil, hempseed oil, raisin seed oil, sunflower seed oil, Semen Maydis oil, Yatall MA, whale oil, hevea oil, tung oil, walnut oil, peanut oil, Canola Oil, Oleum Gossypii semen, the lipid acid of sugarcane lipid acid.
Mixed acid anhydride is also contained in the present invention, that is, and and the acid anhydrides of MGDA and/or GLDA and two or more different carboxylic acids.
In addition, the sequestrant precursor of MGDA and/or GLDA is contained in the present invention, and in described sequestrant precursor, several groups combine, and, not only contains ester, acid amides or anhydride group that is, also contains two or more the mixture in them.Yet in order to be easy to produce, wherein to be converted into the sequestrant precursor of identical ester, acid anhydrides or amide group be preferred to carboxylic acid/carboxylate groups.
Should be understood that, by selecting suitable functional compound, can customize physicals, as visco-elasticity, viscosity and thermostability to meet the requirement of application.
Preferably, the present invention relates to the GLDA ester, even more preferably rudimentary GLDA ester (being the ester of GLDA and C1-C6 alcohol or glycol), the ester of GLDA and C2-C6 alcohol or glycol most preferably, thereby they are to have the liquid that enough low viscosity can be pumped because find, and because their low water solubility is created in hydrolysis slowly in water, and good oil compatibility.
Lower alcohol and glycol, particularly glycol (that is, the C1-C6 glycol) are also preferred because their advantage be after hydrolysis as mutual solvent, while in processing subterranean strata, using described sequestrant precursor, this is favourable.Mutual solvent is the chemical additive used in the subterranean strata of being everlasting is processed, and its oil-soluble, water and acidic group are processed fluid.Usually use in some applications mutual solvent, as remove the heavy hydrocarbon settling, before processing, during or control afterwards the wetting properties of surface in contact, and prevent or destroy emulsion, because they can increase the consistency between hydrophobic and hydrophilic substance.The mutual solvent generally used is ethylene glycol monobutyl ether, is commonly called EGMBE.Lower alcohol and glycol (C1-C6 alcohol and C1-C6 glycol, as methyl alcohol, ethanol, monoethylene glycol, glycol ether, triglycol) are also preferred, because they can be used as hydrate inhibitor.Gas hydrate is ice shape inclusion compound solid, and it is formed at the pressure raise and lower temperature by water and little hydrocarbon in the gentle production operation of oil (that is, the processing of subterranean strata).The temperature that can form hydrate lower than this temperature increases along with the increase of pressure, and this temperature can be up to 25-30 ℃.Gas hydrate is the most common in seabed or cold climate humid gas or heterogeneous (oil/water/gas) pipeline, in these places, they can stop flowing of fluid, if the pressure-temperature condition is suitable, they also can be during drilling well, completion and workover treatment and in gas processing device, the water chemistries injection period of containing in the gas inject pipeline and in the gas lift pipeline forms.Lower alcohol and glycol are at present be used to preventing the most common chemical type of hydrate formation as the thermodynamics hydrate inhibitor.They are by changing the overall thermal mechanical property of fluid systems, and the equilibrium conditions thus gas hydrate formed changes to lower temperature or higher pressure and plays a role.Therefore, can use them to prevent that hydrate from forming, and can also " fusing " existing hydrate sediment.
In another embodiment, oxyalkylated alcohol and oxyalkylated amine are preferred, can bring into play the tensio-active agent function because they have advantages of.
Be known that amine usually has erosion-resisting effect, and for this reason, it is preferred.
Carboxylic acid is preferred, because they provide extra acidity for solution after the acid anhydrides hydrolysis.
In addition, a lot of alcohol has biocidal activity, and therefore, they can improve the biocidal activity of fluid afterwards in hydrolysis, for example, and in disinfectant preparation or in the preparation of the sulfate reduction bacterium in controlling subterranean strata.
Embodiment 1
The preparation of embodiment 1-GLDA ethyl ester
In an embodiment, L-glutamic acid Ν, Ν-oxalic acid and ethylenediamine tetraacetic acid (EDTA) available from Akzo Nobel Functional Chemicals BV (
Product line), methylglycine Ν, Ν-oxalic acid available from BASF Corporation (
Product line).
Embodiment 1a?
The GLDA mono ethyl ester:
Make L-glutamic acid Ν, the backflow of slurry of the sulfuric acid of Ν-oxalic acid and catalytic amount in ethanol 1 hour.By evaporation, remove ethanol, remaining white solid.According to
1H-NMR, the GLDA of this product: the ethyl ester ratio is 1:1.
The product formed has 1.8 pH value (1wt%, in water)
Embodiment 1b GLDA tetra-ethyl ester
SOCl by 4.4 equivalents
2Slowly join 1 equivalent L-glutamic acid Ν, in the ethanol slurry of Ν-oxalic acid.Adding all SOCl
2After, this mixture 1 hour of refluxing, and remove all ethanol and excessive HCl.The material of remaining milk shape, by
1H NMR analyzes this material, and this material is the GLDA tetra-ethyl ester.The pH value of 1% slurry in water is 1.8.
By in this product, adding the ethanol of fresh amounts and 1 equivalent Na
2CO
3, can make the tetraethyl ester product of lower acidity.This mixture is stirred and spends the night, filters, removes ethanol.In order to remove all carbonate, add ether, and after filtration, evaporate described ether.The liquid obtained passes through
1It is the GLDA tetra-ethyl ester that H NMR is accredited as, and the pH value of its 1% slurry in water is approximately 9.
The preparation of a series of GLDA of embodiment 2, MGDA and EDTA ester
Use thionyl chloride (SOCl
2), use the route of embodiment 1b again to synthesize a series of sequestrant esters.Following reaction formula has shown the esterification of simplifying:
According to following universal method, prepare the inner complex ester.Add-on for the preparation of the reactant of concrete inner complex ester is listed in table 1.
The acid of solid inner complex is placed in to the round-bottomed flask with two side necks, and described two side necks are equipped with water cooler and dropping funnel.Add alcohol or the glycol of molar excess, form slurry.With oval magnetic stirring bar, stir this slurry.Because reaction is violent, therefore with dropping funnel, add very lentamente the SOCl that compares excessive 0.5 equivalent with the carboxyl total yield (that is, GLDA4 carboxyl, MGDA3 carboxyl) of sequestrant in this slurry
2.
Table 1: for the synthetic add-on of ester
Then, this mixture is refluxed until then dissolution of solid refluxes this solution other 1 hour.The size that depends on pure chain, total regurgitant time is between 2 to 7 hours.For example, methyl alcohol needs the return time of 2 hours, and the propyl carbinol that refluxed during 7 hours.Subsequently, cooling this solution and with rotatory evaporator with approximately pressure evaporating alcohol or the glycol of 20 millibars.Next, flask is placed in to 40 ℃, approximately in the stove of 1 millibar 24 hours to remove remaining volatile matter.
Total has been synthesized 8 kinds of different inner complex esters, then their hydrolysis properties of test under oilfield conditions:
-methyl alcohol and GLDA-H
4The GLDA-tetramethyl ester
-1-propyl alcohol and GLDA-H
4GLDA-tetrapropyl ester
-n-butyl alcohol and GLDA-H
4GLDA-tetrabutyl ester
-EMGBE(ethylene glycol monobutyl ether) and GLDA-H
4GLDA-tetra-EMGBE esters
-methyl alcohol and EDTA-H
4The EDTA tetra-ethyl ester
-1-propyl alcohol and EDTA-H
4The EDTA-orthocarbonate
-n-butyl alcohol and EDTA-H
4EDTA-tetra-butyl esters
-methyl alcohol and MGDA-H
4The MGDA-trimethyl
Ester purity shown in table 2 is passed through
1H and
13C-NMR measures.In addition, carry out the vision observation to determine the original state of ester, as color, liquid/solid.
In addition, in the situation that possible, the following physical properties of mensuration inner complex ester under 25 ℃:
-viscosity, mPas
-surface tension, mN/m
-density, kg/m
3
By the Brookfield DV-II viscometer determining viscosity that axle 25 is housed, this viscometer is suitable for measuring highly viscous liquid.The principle of operation of DV-II is to drive specific axle, and described axle is dipped in test fluid flow.By the measurements of springs fluid of calibration, resist the viscous resistance of axle.Torque calculation viscosity by speed of rotation, type and axle.In addition, with the pressure in bubbles tonometer, measure surface tension.Tonometer produces bubble and they is blown over to the kapillary be immersed in sample liquids with constant rate of speed.Pressure (P) in bubble constantly increases, and when bubble has radius accurately corresponding to the complete semisphere of capillary radius, obtains maximum value.
By following bubble formation, changing each step in bubble radius and corresponding pressure, dynamic surface tension can be used for the Laplace equation of the reduced form of spherical bubbles in liquid to be determined:
Equation: σ=(Δ PmaxRcap)/2
Wherein: σ=dynamic surface tension
Δ Pmax=maximum pressure drop
The Rcap=capillary radius
Density can weighting method be determined, in the valinche of weighing, slowly accurately drawn 0.50ml inner complex ester and, by the gross weight of weigh this valinche and inner complex ester, can determine the weight of 0.50ml inner complex ester.
The vision observation of synthetic ester physicals and the result of measuring have been shown in following table 2.
Table 2: the performance of synthetic ester
N.p.=can't measure.
Because high viscosity, can not measure the density of EDTA-tetrapropyl and butyl ester, still, this density is apparently higher than water.
All inner complex methyl ester are all viscosity and not tractable, and the character of EDTA-tetramethyl ester is more as solid.With butyl ester, compare, all methyl ester are dissolved easilier, and butyl ester is water insoluble.The character of propyl group, butyl and EMGBE inner complex ester more is similar to liquid.The butyl ester of EDTA and GLDA demonstrates two-phase, organic phase and water under low pH condition.Surprisingly, all GLDA esters except methyl ester demonstrate extremely significantly two-phase system in aqueous environment, and if acutely shake bottle, the more easily emulsification in water layer of EDTA ester.In contrast, the GLDA layer keeps complete.In addition, between the viscosity of the GLDA ester with comparable ester group and EDTA ester, has marked difference; The character of GLDA ester more is similar to the fluid of good flow than EDTA ester.This relatively low viscosity of GLDA ester is very large advantage in operation, because it can be pumped in rock stratum at an easy rate.
The proportion of all inner complex esters or density are all on the proportion of water, and this is implying that heavier inner complex ester will sink, and this is an advantage in oil well for example, because fluid will more easily arrive target area.The GLDA ester shows this advantage especially.
In table 3, provided the summary of physical condition difference.
Table 3: the solubleness of inner complex ester in water
The hydrolysis of embodiment 3 inner complex esters
In some experiments, studied the hydrolysis of the inner complex ester of embodiment 2.At first, use
1H and
13C-NMR measures the hydrolysis rate of inner complex ester.The NMR result shows, the hydrolysis of GLDA and MGDA methyl ester can be interpreted as slowly discharging.Under 70 ℃ approximately after 2 days, these inner complex esters present almost completely hydrolysis.Secondly, after hydrolysis rate, then measure Fe-TSV, described Fe-TSV has provided the concentration of the inner complex acid discharged.In order to measure Fe-TSV, the inner complex ester is joined in the softening water in 5 milliliters of phials, obtain the ester concentration of 20wt%.By jolting in ultrasonic bath and processing, carry out this mixture of continuous homogenization.Subsequently, this phial is placed in the stove under 90 ℃ to the condition with simulation well.After certain time interval, take out sample, and on Fe-TSV analytic sample.The per-cent of hydrolysis is defined as:
Inner complex concentration when initial by the add-on calculating of ester.By this value of purity correction that NMR records, suppose that corresponding inner complex 100% transforms.
The impact of embodiment 3a-sequestrant on hydrolysis
Hydrolysis rate result with inner complex ester of methyl group is presented in Fig. 1.Can clearly be seen that, the EDTA-methyl ester is fast more a lot of than corresponding GLDA or the hydrolysis of MGDA-methyl ester.Also find, GLDA-tetramethyl ester and MGDA-trimethylammonium ester have almost identical hydrolysis rate.Yet MGDA only discharges 3 methanol groups, and GLDA can discharge 4 methanol groups within the identical time.Higher methanol concentration can form the mode that prevents that more effectively hydrate from forming.
Importantly, when hydrolysis EDTA ester, form solid EDTA.Obviously, reached the solubility limit of ETDA acid.GLDA and MGDA do not have such shortcoming, because the solubleness of GLDA and MGDA acid is obviously higher.
The impact of embodiment 3b alcohol on hydrolysis
As in Fig. 2, seeing, the release of GLDA is subject to the impact of alcohol groups length.The alcohol groups of GLDA ester is longer, and hydrolysis rate is slower.The difference of hydrolysis rate clearly illustrates that, can customize according to the demand of well the release of GLDA acid and alcohol groups.
The methyl of embodiment 3c GLDA and EDTA and the comparison between propyl diester
Fig. 3 has provided the representative of the hydrolysis of ester.As in embodiment 3b, hydrolysis rate depends on the length of the alcohol groups that is used to form ester.It should be noted that the GLDA ester counterpart of EDTA ester hydrolysis faster than them.Although aspect hydrolysis rate, there is no significant difference at first, yet approximately after 3 days, the esterolytic speed of EDTA is compared in the esterolytic speed of GLDA, greatly increases.
The impact of embodiment 3d pH value
The ester synthetic by the thionyl chloride route is acid, because in reaction process, formed HCl salt.Therefore the pH value will be in about 1 left and right when being dissolved in this ester in water.Under downhole condition, due to the interaction with other chemical substance, the pH value may be higher.In order to determine the impact of pH value, with caustic alkali, sample being adjusted to the pH value is 7.The pH value has been shown in Fig. 4 and the GLDA/EDTA-propyl diester has been discharged to the impact of sequestrant.Hydrolysis rate is slight decline along with the increase of pH value.
Claims (15)
1. sequestrant glutamic acid N, N-oxalic acid (GLDA) and/or methylglycine N, the sequestrant precursor of N-oxalic acid (MGDA), wherein at least one hydroxy-acid group exists with carboxylic acid derivative, and described carboxylic acid derivative selects free acid amides, acid anhydrides, ester, its combination, and the group of salt composition, condition is the triethyl that described sequestrant precursor is not GLDA, the triethyl list tertiary butyl ester of GLDA, the tri-tert ester of GLDA, the monobenzyl tri-tert ester of GLDA, the any ester or the acid amides that contain the azacycloalkyl hydrocarbyl group, the any acid amides that contains the vitamin H group, contain any acid amides based on the amide group of aminoethylamino formyl radical, (S)-2,2 '-(1-benzyloxy)-1,5-dioxo-5-(Propargyl amino) penta-2-base azane two bases-oxalic acid diethyl ester, 2,2 '-(5-(3-azido-propyl group amino)-1-(benzyloxy)-1,5-dioxo-penta-2-base azane, two bases-oxalic acid diethyl ester, the trimethyl of MGDA, the monomethyl ester dimethylformamide of MGDA, the dibenzyl ester of MGDA, the dibenzyl list tertiary butyl ester of MGDA, the di-t-butyl ester of MGDA, the di-t-butyl monobenzyl ester of MGDA, N, two (benzyloxycarbonyl the methyl)-N ' of N--methoxycarbonyl methyl-ala amide or N, two (uncle-butoxy carbonyl)-N ' of N--methoxycarbonyl methyl-ala amide and be fixed on the GLDA ester on gel, and described acid amides is not the acid amides of ammonia.
2. sequestrant precursor as claimed in claim 1, wherein said carboxylic acid derivative is pure ester, and described alcohol is selected from the fatty alcohol that contains 1-12 carbon atom, and this fatty alcohol optionally can contain extra hydroxyl, amine and/or ether group.
3. sequestrant precursor as claimed in claim 1 or 2, wherein said carboxylic acid derivative is the amide group of amine, and described amine is selected from the aliphatic amine that contains 1-12 carbon atom, and this aliphatic amine optionally can contain extra hydroxyl, carboxylic acid, amine and/or ether group.
4. sequestrant precursor as claimed any one in claims 1 to 3, wherein said carboxylic acid derivative is the anhydride group of carboxylic acid, described carboxylic acid is selected from lipid acid and contains the aliphatic carboxylic acid of 1-12 carbon atom, and described carboxylic acid optionally can contain extra hydroxyl, amine, carboxylic acid and/or ether group.
5. the fluid that contains the described sequestrant precursor of any one and liquid in claim 1 to 4.
6. fluid as claimed in claim 5, wherein said liquid is liquid, aqueous.
7. sequestrant precursor or contain acidity that the fluid of this sequestrant precursor and liquid postpones therein or the purposes in the sequestering power useful application, described sequestrant precursor is selected from the glutamic acid N that at least one hydroxy-acid group wherein exists with carboxylic acid derivative, N-oxalic acid (GLDA) and/or methylglycine N, N-oxalic acid (MGDA), the group that described carboxylic acid derivative selects free acid amides, acid anhydrides, ester, its combination and salt thereof to form, described application examples is if be scale removal, bleaching, clean and process the subterranean strata of oil-containing and/or gas.
8. the purposes of sequestrant precursor as claimed in claim 7, it is the purposes in processing subterranean strata, wherein said carboxylic acid derivative is the ester of C1-C6 alcohol or C1-C6 glycol, wherein said sequestrant precursor is hydrolyzed and discharges alcohol or glycol at least partly, and helps the inhibition of hydrate and/or as mutual solvent.
9. process the method for subterranean strata, wherein sequestrant precursor or the fluid that contains described sequestrant precursor are introduced in described rock stratum, described sequestrant precursor is selected from the glutamic acid N that at least one hydroxy-acid group wherein exists with carboxylic acid derivative, N-oxalic acid (GLDA) and/or methylglycine N, the group that N-oxalic acid (MGDA), described carboxylic acid derivative select free acid amides, acid anhydrides, ester, its combination and salt thereof to form.
10. method as claimed in claim 9, when wherein said sequestrant precursor is introduced in described rock stratum or afterwards, it is hydrolyzed at least partly.
11. method as claimed in claim 10, wherein said fluid contain the reagent that helpful described sequestrant precursor is hydrolyzed to discharge GLDA and/or MGDA in addition, as enzyme, alkali or acid.
12. method as described as any one in claim 9 to 11, wherein said sequestrant precursor are the esters of GLDA.
13. method as claimed in claim 12, wherein said sequestrant precursor are the esters of GLDA and C1-C6 alcohol or C1-C6 glycol.
14. method as described as any one in claim 9 to 13, the pH value of wherein said fluid is between 1 to 7.
15. the described method of any one in claim 9 to 14, wherein said subterranean strata contacts with the temperature of described fluid between 25 ℃ to 204 ℃.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161445291P | 2011-02-22 | 2011-02-22 | |
| US61/445,291 | 2011-02-22 | ||
| EP11158650.9 | 2011-03-17 | ||
| EP11158650 | 2011-03-17 | ||
| PCT/EP2012/052824 WO2012113738A1 (en) | 2011-02-22 | 2012-02-20 | Chelating agent precursors, fluids containing them, and their use |
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| CN103415502B CN103415502B (en) | 2016-03-02 |
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| Country | Link |
|---|---|
| US (1) | US9556378B2 (en) |
| EP (1) | EP2678309B1 (en) |
| CN (1) | CN103415502B (en) |
| BR (1) | BR112013020716A2 (en) |
| WO (1) | WO2012113738A1 (en) |
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| US9027647B2 (en) | 2006-08-04 | 2015-05-12 | Halliburton Energy Services, Inc. | Treatment fluids containing a biodegradable chelating agent and methods for use thereof |
| US9120964B2 (en) * | 2006-08-04 | 2015-09-01 | Halliburton Energy Services, Inc. | Treatment fluids containing biodegradable chelating agents and methods for use thereof |
| US8567504B2 (en) | 2006-08-04 | 2013-10-29 | Halliburton Energy Services, Inc. | Composition and method relating to the prevention and remediation of surfactant gel damage |
| US9127194B2 (en) | 2006-08-04 | 2015-09-08 | Halliburton Energy Services, Inc. | Treatment fluids containing a boron trifluoride complex and methods for use thereof |
| US8881823B2 (en) | 2011-05-03 | 2014-11-11 | Halliburton Energy Services, Inc. | Environmentally friendly low temperature breaker systems and related methods |
| US9334716B2 (en) | 2012-04-12 | 2016-05-10 | Halliburton Energy Services, Inc. | Treatment fluids comprising a hydroxypyridinecarboxylic acid and methods for use thereof |
| US9670399B2 (en) | 2013-03-15 | 2017-06-06 | Halliburton Energy Services, Inc. | Methods for acidizing a subterranean formation using a stabilized microemulsion carrier fluid |
| US9745504B2 (en) | 2013-03-21 | 2017-08-29 | Halliburton Energy Services, Inc. | Wellbore servicing compositions and methods of making and using same |
| US9512348B2 (en) | 2013-03-28 | 2016-12-06 | Halliburton Energy Services, Inc. | Removal of inorganic deposition from high temperature formations with non-corrosive acidic pH fluids |
| GB2519388B (en) | 2014-03-04 | 2015-10-28 | Cleansorb Ltd | Method for treatment of formation damage using cyclodextrin |
| US20170369768A1 (en) | 2016-06-24 | 2017-12-28 | Cleansorb Limited | Shale Treatment |
| US11618849B2 (en) | 2016-06-24 | 2023-04-04 | Cleansorb Limited | Shale treatment |
| WO2018236221A2 (en) * | 2017-06-03 | 2018-12-27 | Can Holding B.V. | Neurodegenerative peptide deposit dissolution |
| CN108102624B (en) * | 2017-12-14 | 2021-03-19 | 中国石油天然气集团有限公司 | Neutral blockage removal treating agent and preparation method thereof |
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| US9556378B2 (en) | 2017-01-31 |
| EP2678309B1 (en) | 2015-11-04 |
| CN103415502B (en) | 2016-03-02 |
| EP2678309A1 (en) | 2014-01-01 |
| WO2012113738A1 (en) | 2012-08-30 |
| BR112013020716A2 (en) | 2016-10-18 |
| US20130331304A1 (en) | 2013-12-12 |
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